Hydrogenation derivatives of difurfuralacetone



Patented Oct. 27, 1953 liHYDROGENATION DERIVATIVES .OF

. EDIFURFURALAOETONE Kliem 'AlexamlerandLester E. Sc'hniepp, Peoria, Ill., assignorsto' the United Statesof America as represented by the Secretary of Agriculture .NoDrawing. Application June 22, 1951, v

. Serial No. 233,008

' 5 Claims.

Y (Granted under Title 35, U. S. Code (1952),

sec. 266) The invention herein described may be manufactured and used by or for the Government of the United States of America for governmental purposes throughout the world without the payment to us of any royalty thereon.

This invention relates to the novel chemical compounds, 2-(fl furylethyl) 1,6 dioxaspiro- [4.4] nonane (I), 2-(fi-tetrahydrofurylethyl) 1,6-dioxaspiro-[4.4l nonane (II), l-tetr'ahydrofuryl-3,6,9 nonanetriol (III) and 1,4,7,10,13-tridecanepentaol (IV). These chemicals .are derived from difurfuralacetone by controlled hydrogenation.

Difurfuralacetone is-one of the two simple condensation products of furfural and acetone. It maybe made by mixing furfural and acetone in 2z-1 molar ratio, cooling the mixture and adding sodium hydroxide. The condensation product crystallizes after standing. =It has the following structural formula:

According to our invention, difur'furalacetone is subjected to catalytic hydrogenation, 'preferably with a copperchromite or nickel-onkieselguhr catalystin vsucha manner that the hydrogenation occurs stepwise. The .desired products of eachs'tep of hydrogenation-.m'ay be isolated vfrom the reaction mixture .and subsequently further hydrogenated to produce prod- .ucts dfa greater degree ofv hydrogenation.

The catalytic hydrogenation of difurfuralacetone produces a mixture .of '(I) and 1,5-difurylpentanol-B, when a copper chromite-type catalyst is employed. IFurther hydrogenation of the crude hydrogenation mixture or 1,5-difurylpentanol-3 with a nickel catalyst, such as Raney nickel, results 'in compounds saturated in the furyl portion of the molecule. Thus, hydrogenation of (I) gives (II); 1.5-difurylpentanol-3 gives 1,5- ditetrahydrofurylpentanol-3; and the mixture from copper chromite catalyzed reduction, when further hydrogenated with a nickel catalyst, gives a mixture of (II) and 1,5-ditetrahydrofurylpentanol-3, the latter being usually the main fraction.

The foregoing stepwise hydrogenations are effected in the substantial absence of water. If water is present, however, the hydrogenation is accompanied by rupture of the oxygen-containing rings. Thus, the hydrogenation of 1,5-difurylpentanol-3 in the presence of substantial amounts of water results in (III) and (IV). The same products result. fromthe hydrogenation .of @9512), or the .crudereaction mixture containing 1.5- idifurylpentanol-b. and (I).

.JI'his. lattertype of .ireaction may be :termed 22a combined hydrogenation and hydrolysis, even though .the actual .chemical mechanisms involved .have-znot-been determined exactly.

The compounds of .this invention have-the :fol-

lowing "structural formulae:

l O 1CH2CH2OHCHzCHzfiDHQHtQHiCHBOH H OH Iv -:omomcmcHomomonomcHwHoHicHicHs OH OH OH H son They are useful as intermediates in the chemical industry, in the field of solvents andplasticizers,

hydraulic fluids, lubricant additiveslhumectants,

and medicinals. The following. specificexamples illustrate .the invention. The methods of prep.- aration described in these examples are .not'intended to be limiting inasmuch as variationof temperatures, reaction times, catalysts, and .the like will readily occur to those skilled in the.ar.t.

Example v1 ving at 84-85 C. This fraction consisted of (I) AnaL: Calcd. for C1sH1aOa: C, 70.2; H, 8.16; OH, 0.00. Found: C, 69.7; H, 8.02; 0-H, 0.00.

tion of two double bonds. moved by filtration, and the filtrate fractionated.

vOH, 20.73.

Example 2 To the filtrate obtained by removing the copper chromite catalyst from a solution, hydrogenated as in the example above, was added 7 g. of Raney nickel catalyst. The material was then reacted with hydrogen at 32-140 C. for 2 hrs. The catalyst was removed by filtration, and fractionation of the lower boiling component's gave 11.2 g. of (II) a colorless liquid, B. P. 90-95 C. (0.09 mm.) 11 1.4720; (1 1.0403. It is a mobile liquid of mild, pleasant odor, only slightly soluble in water at room temperature.

Anal.: Calcd. for CHI-12203: C, 68.95; H, 9.80; OH, 0.0. Found: C, 68.65; H, 9.66; 01-1, 0.0.

The main fraction consisted of 1,5-ditetrahydrofurylpentanol-3.

Example 3 (I), prepared by the method of Example 1 (49.6 g.) was admixed with g. of Raney nickel catalyst and 214 ml. of absolute ethanol. The mixture was hydrogenated at 40-117 C. for 3 /2 hrs. The amount of hydrogen absorption was slightly greater than that required for satura- The catalyst was re- The main fraction, 32.2 g., was a colorless liquid, B. P. 96101 C. (0.17 mm.). It was (II), 11. 1.4720, identical with the product of Example 2.

In the following example, there is illustrated the preparation of (III) and (IV), employing 1,5difurylpentanol-3 as the starting material. As previously noted, we may substitute instead, the crude reaction mixture such as obtained in Example 1. In this example, the presence of substantial amounts of water is necessary, together with more intense catalytic effect of the nickel-type catalysts. As illustrated, we prefer nickel-on-kieselguhr catalysts, and we prefer to carry out the reaction in an aqueous medium. It is to be understood that the isolated pentanol or the unfractionated hydrogenation mixture containing the pentanol as the main constituent, such as obtained in Example 1, may be substituted with no substantial difference in procedure. Likewise, the same results may be obtained by substituting (I) Example 4 One hundred sixty-five grams (0.075 mole) of 1,5-difurylpentanol-3, 220 g. of water, 7.0 g. of

'nickel-on-kieselguhr catalyst and a trace of 90 percent formic acid (approximately 0.3 ml.) was reacted with hydrogen at 200-210 C. for 5 hrs.

tion, and the reaction product was subjected to fractional distillation at 0.16 mm. The fraction boiling between 191-200 C. amounted to 65.0 g. It was (III), B. P. 194 C., (0.15 mm), n 1.4913, 11, 1.076.

Anal: Calcd. for: 0131-12604: Found: C, 63.1; H,

C, 63.4; H, 10.63; 10.7; OH, 20.59.

4 Example 5 The undistillable residue from Example 4 above amounting to 30.1 g. was washed with acetone to give a solid product which was recrystallized and identified as (IV) Anal: Calcd. for: 01231 128051 C, 59.1; H, 10.67; OH, 32.16 Found: C, 59.0; H, 10.3; 01-1, 32.8.

In place of the 1,5-difurylpentanol-3 employed in Example 4 above, we may substitute either the hydrogenation mixture produced in Example 1 or the (I) product.

The product of Example 4 is soluble in acetone and water, whereas the product of Example 5 is soluble in water, but insoluble in cold acetone.

We claim:

1. A compound selected from the group consisting of and GHzC H2O Hlc HG memo HO H20 H20 Ho Hzomo H1 on OH OH H OH OH OH I OH OH OH OH OH lyst to produce a reaction mixture containing 2 (6 tetrahydrofurylethyl) 1,6 dioxaspiro [4.4] nonane, adding water to the reaction mixture and further hydrogenating to produce a reaction mixture containing l-tetrahydrofuryl- 3,6,9 nonanetriol and 1,4,7,l0,13-tridecanepentaol in admixture and separating l-tetrahydrofuryl- 3,6,9 nonanetriol by distillation fractionation.

5. The method comprising subjecting 1,5-difurylpentanol-B to hydrogen in the presence of a nickel catalyst to produce l-tetrahydrofuryl- 3,6,9 nonanetriol, separating the catalyst from the reaction mixture and recovering l-tetrahydrofuryl-3,6,9 nonanetriol by distillation fractionation.

KLIEM ALEXANDER. LESTER E. SCHNIEPP.

No references cited. 

1. A COMPOUND SELECTED FROM THE GROUP CONSISTING OF 